A high-pressure-resistant and moisture-resistant organic silicon sealant for new energy power systems

Abstract

The present application relates to the technical fields of adhesive preparation and application, in particular to a high-pressure and moisture-resistant organic silicon sealant for new energy power systems. The organic silicon sealant is composed of component A, component B and platinum-ion liquid catalyst. Component A includes modified boron-nitrogen heterocyclic polysiloxane, fluorine-containing siloxane composite filler, 3-epoxypropoxypropyl triethoxysilane and 2,5-dimethyl hexyne diol. Component B includes end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide and gamma-methacryloyloxypropyl trimethoxysilane. The platinum-ion liquid catalyst is prepared from chloroplatinic acid and 1-butyl-3-methyl imidazole hexafluorophosphate. The high-pressure and moisture-resistant organic silicon sealant provided by the present application has better heat conductivity and high-pressure resistance. After 1200h of hygrothermal aging treatment, the retention rates of thermal conductivity and volume resistivity are both greater than 91%, and the sealant has good extreme hygrothermal weather resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesive preparation and application, and particularly relates to a high-pressure and moisture-resistant organic silicon sealant for new energy power systems. BACKGROUND

[0002] With the increasing pressure of reducing carbon emissions and the improvement of people's energy conservation and environmental protection consciousness, the automobile industry is undergoing a new industrial revolution, and new energy vehicles will become the future development trend. Due to regional differences, the vehicle environment in different regions is very different, resulting in that some electronic components are in a harsh environment of high temperature, cold and hot cycle, moisture, dust, dirt, mold, mechanical impact and vibration for a long time during use, which is easy to cause danger due to short circuit of the power system caused by sealing failure. Therefore, the sealing glue for new energy power systems needs to meet the technical requirements of high voltage resistance and strong weather resistance.

[0003] The prior art with publication number CN115558451B provides a power battery sealing material, the A component preparation raw materials include: silane-modified polyether 45-75 parts, crosslinking aid 15-20 parts, filler 15-30 parts, reinforcing agent 15-40 parts, organic phosphorus 0.5-5 parts, plasticizer 10-20 parts, organic amine 5-15 parts; the B component preparation raw materials include: epoxy resin 30-60 parts, filler 15-30 parts, inorganic salt 15-40 parts, organic phosphorus 0.5-5 parts, plasticizer 10-20 parts, water removal agent 1-10 parts, thixotropic agent 5-15 parts, tin-containing compound 2-8 parts; it uses traditional silane modification, and the high-pressure resistance performance is limited. The prior art with publication number CN116589969A discloses a low-hardness lightweight flame-retardant sealant, which is prepared by mixing the following raw materials in parts by weight: 20,000 viscosity hydroxyl-terminated polydimethylsiloxane polymer 100 parts, high viscosity hydroxyl-terminated polydimethylsiloxane polymer 70-120 parts, plasticizer 70-130 parts, flame-retardant filler 180-240 parts, lightweight additive 45-70 parts, thixotropic agent 4-10 parts, crosslinking agent 10-20 parts, curing agent 2-5 parts, and organic titanium catalyst 5-10 parts. This scheme realizes lightweight, but does not solve the stability problem in a humid heat environment.

[0004] The existing organic silicon sealant still has the following technical bottlenecks: the thermal conductivity network is not complete, the thermal conductivity is low; the interface bonding force between the filler and the matrix is insufficient, and the interface defects are easy to be broken down under the action of high voltage electric field; long-term high temperature and high humidity environment leads to a large performance decline. SUMMARY

[0005] In order to solve the above problems existing in the prior art, the application provides a high-pressure and moisture-resistant organic silicone sealant for new energy power systems, and the following purposes are achieved: the prepared high-pressure and moisture-resistant organic silicone sealant for new energy power systems has the advantages of good heat conductivity, high pressure resistance and extreme moisture and heat resistance.

[0006] In order to achieve the above-mentioned purposes, the technical scheme adopted is as follows:

[0007] The application provides a high-pressure and moisture-resistant organic silicone sealant for new energy power systems, which is composed of component A, component B and a platinum-ion liquid catalyst; the mass ratio of the amount of component A to the amount of component B is (2.8-3.6):1, and the amount of the platinum-ion liquid catalyst is 0.55%-0.71% of the mass of component A.

[0008] The components of component A include modified boron-nitrogen heterocyclic polysiloxane, fluorosiloxane composite filler, 3-epoxypropoxypropyl triethoxysilane and 2,5-dimethyl hexyne diol; the mass ratio of the amount of modified boron-nitrogen heterocyclic polysiloxane to the amount of fluorosiloxane composite filler to the amount of 3-epoxypropoxypropyl triethoxysilane is (18-26.5):(12.8-17.5):1; and the amount of 2,5-dimethyl hexyne diol is 0.1-0.2‰ of the mass of modified boron-nitrogen heterocyclic polysiloxane.

[0009] The components of component B include end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide and gamma-methacryloyloxypropyl trimethoxysilane; the mass ratio of the amount of end-hydrogen silicone oil to the amount of perfluorinated nonyl polydimethylsiloxane to the amount of nano zinc oxide to the amount of gamma-methacryloyloxypropyl trimethoxysilane is (3-4):(1.5-2):(2-2.8):1.

[0010] The platinum-ion liquid catalyst is prepared from chloroplatinic acid and 1-butyl-3-methyl imidazole hexafluorophosphate phosphate, and the mass ratio of the amount of chloroplatinic acid to the amount of 1-butyl-3-methyl imidazole hexafluorophosphate phosphate is 1:8.

[0011] The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane and boron-nitrogen benzene; the mass ratio of octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane and boron-nitrogen benzene is (12-13.3):(7.2-8):1.

[0012] The fluorosiloxane composite filler is prepared from nano zirconium carbide, nano aluminum nitride and tridecafluorooctyl trimethoxysilane; the mass ratio of the amount of nano zirconium carbide to the amount of nano aluminum nitride to the amount of tridecafluorooctyl trimethoxysilane is (2.2-5):(6-8):1.

[0013] The application further provides a preparation method of the high-pressure and moisture-resistant heat-resistant organic silicone sealant for new energy power systems.

[0014] Step one, preparation of modified boron-nitrogen heterocyclic polysiloxane

[0015] Add octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane and boron-nitrogen benzene into a reactor, replace with high-purity nitrogen gas, and heat to 125-135 DEG C under the protection of nitrogen atmosphere, and keep the temperature for 6-10 hours; open the stirring during the whole reaction process, and the stirring rate is 200 r / min; after the reaction is completed, perform vacuum distillation on the reaction liquid under the condition of vacuum degree ≤-0.08 MPa and temperature 120 DEG C, and after removing the low-boiling substances, the obtained substrate is the modified boron-nitrogen heterocyclic polysiloxane.

[0016] Step two, preparation of fluorine-containing siloxane composite filler

[0017] Add nano zirconium carbide, nano aluminum nitride, tridecafluorooctyl trimethoxysilane and ethanol into an ultrasonic tank, stir uniformly to prepare a suspension; ethanol is used as a dispersant, and the addition amount is 10 times the mass of tridecafluorooctyl trimethoxysilane; set the ultrasonic power to 300-350 W, and ultrasonically treat the suspension under the condition of temperature 45-60 DEG C for 30-60 min; filter the suspension after ultrasonic treatment, retain the solid, and after vacuum drying, the obtained solid is the fluorine-containing siloxane composite filler; the vacuum drying condition is temperature 90 DEG C, vacuum degree ≤-0.08 MPa, and drying time 1 h.

[0018] Step three, preparation of component A

[0019] Add the modified boron-nitrogen heterocyclic polysiloxane, the fluorine-containing siloxane composite filler and 3-epoxypropoxypropyl triethoxysilane into a double-planetary stirrer, stir under the condition of temperature 90 DEG C and vacuum degree ≤-0.08 MPa for 2-3 h, and the stirring speed is 30 r / min; after the stirring is completed, naturally cool, add 2,5-dimethyl hexyne diol when the temperature is ≤45 DEG C, and after uniform stirring, component A is obtained.

[0020] Step four, preparation of component B

[0021] Mix nano zinc oxide and gamma-methacryloyloxypropyl trimethoxysilane, and then add into an ultrasonic tank, ultrasonically treat for 30-60 min at a power of 300-400 W, and the obtained zinc oxide-silane reaction liquid; add the zinc oxide-silane reaction liquid, hydrogen-terminated silicone oil and perfluorononyl polydimethylsiloxane into a high-speed disperser, disperse under the condition of temperature 60-70 DEG C and rotating speed 2000 r / min for 1-2 h, and component B is prepared.

[0022] Step five, compounding and defoaming

[0023] The A component is combined with the B component at a weight ratio of (2.8-3.6):1, and a platinum-ionic liquid catalyst is added dropwise to obtain a mixed solution, the mixed solution is added to a static mixer and mixed uniformly, and is degassed under a vacuum degree of ≤-0.09 MPa for 20 min, thereby obtaining the high-pressure-resistant and moisture-resistant type silicone sealant.

[0024] The high-pressure-resistant and moisture-resistant type silicone sealant provided by the application has a thermal conductivity of 1.94-2.37 W / (m·K), a breakdown voltage of 38.5-40.2 kV / mm, and a volume resistivity of 2.5×10 14 14 Ω·cm, which indicates that the high-pressure-resistant and moisture-resistant type silicone sealant provided by the application has better thermal conductivity and high-pressure resistance; after 1200 h of hygrothermal aging treatment, the retention rates of the thermal conductivity and the volume resistivity are both >91%, which shows that the high-pressure-resistant and moisture-resistant type silicone sealant has good extreme hygrothermal weather resistance. DETAILED DESCRIPTION

[0025] The nano-zirconium carbide used in the application has a particle size of 50-100 nm, the nano-aluminum nitride has a particle size of 100-200 nm, the nano-zinc oxide has a particle size of 100-200 nm, the perfluorinated nonyl polydimethylsiloxane has a substitution degree of 50%-60% and an average molecular weight of 40000-60000, the platinum-ionic liquid catalyst is prepared from chloroplatinic acid and 1-butyl-3-methylimidazolium hexafluorophosphate, and the mass ratio of the amount of chloroplatinic acid to the amount of 1-butyl-3-methylimidazolium hexafluorophosphate is 1:8, and the end-hydrogen silicone oil has a viscosity of 500 mPa·s, a molecular weight of 17200, and a density of 0.97 g / cm 3 .

[0026] To make the object, technical solutions and advantages of the application clearer, the embodiments of the application will be further described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the application, and are not used to limit the application.

[0027] Example 1: A high-pressure-resistant and moisture-resistant type silicone sealant for new energy power systems

[0028] A high-pressure-resistant and moisture-resistant type silicone sealant for new energy power systems is composed of an A component, a B component and a platinum-ionic liquid catalyst, the mass ratio of the amount of the A component to the amount of the B component is 3:1, and the amount of the platinum-ionic liquid catalyst is 0.66% of the mass of the A component.

[0029] ​The components of the A component include modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, 3-epoxypropoxypropyl triethoxysilane, and 2,5-dimethyl hexyne diol; the mass ratio of the modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, and 3-epoxypropoxypropyl triethoxysilane is 20:15:1; the amount of 2,5-dimethyl hexyne diol is 0.2‰ of the mass of the modified boron-nitrogen heterocyclic polysiloxane.

[0030] The components of the B component include end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane; the mass ratio of the end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane is 4:1.5:2.5:1.

[0031] The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene; the mass ratio of the octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene is 12.5:7.5:1.

[0032] The fluorosilicone composite filler is prepared from nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane; the mass ratio of the nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane is 5:6:1.

[0033] A preparation method of a high-pressure and moisture-resistant type organic silicone sealant for a new energy power system:

[0034] Step one, preparation of modified boron-nitrogen heterocyclic polysiloxane

[0035] Octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene are added to the reactor; high-purity nitrogen gas is introduced into the kettle for replacement, and the temperature is raised to 135℃ under the protection of a nitrogen atmosphere; the reaction is kept for 6h; the stirring rate is 200r / min during the whole reaction process. After the reaction is completed, the reaction liquid is subjected to vacuum distillation under the conditions of a vacuum degree ≤-0.08MPa and a temperature of 120℃; after the low-boiling substances are removed, the obtained substrate is the modified boron-nitrogen heterocyclic polysiloxane.

[0036] Step two, preparation of fluorosilicone composite filler

[0037] The nanometer zirconium carbide, nanometer aluminum nitride, tridecafluoro octyl trimethoxysilane and ethanol are added into an ultrasonic tank and stirred uniformly to prepare a suspension; the ethanol is used as a dispersant, and the amount of the ethanol is 10 times of the mass of the tridecafluoro octyl trimethoxysilane. The suspension is ultrasonically treated for 60 min at a temperature of 50 DEG C and under the condition of an ultrasonic power of 350 W. The suspension after the ultrasonic treatment is filtered, and the solid is retained. The obtained solid is vacuum dried to obtain a fluorine-containing siloxane composite filler. The vacuum drying is performed under the condition of a temperature of 90 DEG C, a vacuum degree of less than or equal to -0.08 MPa and a drying time of 1 h.

[0038] Step three, preparation of A component

[0039] The modified boron-nitrogen heterocyclic polysiloxane, the fluorine-containing siloxane composite filler and 3-epoxypropoxypropyl triethoxysilane are added into a double planetary stirrer, and stirred for 2.5 h under the condition of a temperature of 90 DEG C, a vacuum degree of less than or equal to -0.08 MPa and a stirring speed of 30 r / min. After the stirring, the temperature is naturally reduced, and 2,5-dimethyl hexyne diol is added when the temperature is less than or equal to 45 DEG C. After the stirring, the A component is obtained.

[0040] Step four, preparation of B component

[0041] The nanometer zinc oxide and gamma-methacryloyloxypropyl trimethoxysilane are uniformly mixed and then added into an ultrasonic tank. The zinc oxide-silane reaction liquid is obtained by ultrasonic treatment for 60 min under the condition of a power of 300 W. The zinc oxide-silane reaction liquid, hydrogen-terminated silicone oil and perfluorinated nonyl polydimethylsiloxane are added into a high-speed disperser, and dispersed for 2 h under the condition of a temperature of 65 DEG C and a rotating speed of 2000 r / min to prepare the B component.

[0042] Step five, compounding and defoaming

[0043] The A component and the B component are compounded in a weight ratio of 3:1, and a platinum-ionic liquid catalyst is added dropwise to obtain a mixed liquid. The mixed liquid is added into a static mixer and uniformly mixed. The high-pressure and moisture-resistant type silicone sealant is prepared by defoaming for 20 min under the condition of a vacuum degree of less than or equal to -0.09 MPa.

[0044] Example 2: A high-pressure and moisture-resistant type silicone sealant for new energy power systems

[0045] The high-pressure and moisture-resistant type silicone sealant for new energy power systems is composed of an A component, a B component and a platinum-ionic liquid catalyst. The mass ratio of the amount of the A component to the amount of the B component is 2.8:1, and the amount of the platinum-ionic liquid catalyst is 0.71% of the mass of the A component.

[0046] The components of the A component include modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, 3-epoxypropoxypropyl triethoxysilane, and 2,5-dimethyl hexyne diol; the mass ratio of the modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, and 3-epoxypropoxypropyl triethoxysilane is 25:17.5:1; the amount of 2,5-dimethyl hexyne diol is 0.1 ‰ of the mass of the modified boron-nitrogen heterocyclic polysiloxane.

[0047] The components of the B component include end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane; the mass ratio of the end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane is 3.3:1.7:2:1.

[0048] The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene; the mass ratio of the octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene is 12:7.2:1.

[0049] The fluorosilicone composite filler is prepared from nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane; the mass ratio of the nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane is 3.5:7.5:1.

[0050] A preparation method of a high-pressure and moisture-resistant type organic silicone sealant for a new energy power system:

[0051] Step one, preparation of modified boron-nitrogen heterocyclic polysiloxane

[0052] Octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene are added to the reactor; high-purity nitrogen gas is introduced into the kettle for replacement, and the temperature is raised to 125℃ under the protection of a nitrogen atmosphere; the reaction is kept for 10 hours; the stirring rate is 200 r / min during the whole reaction process. After the reaction is completed, the reaction liquid is subjected to vacuum distillation under the conditions of a vacuum degree ≤-0.08 MPa and a temperature of 120℃; after the low-boiling substances are removed, the obtained substrate is the modified boron-nitrogen heterocyclic polysiloxane.

[0053] Step two, preparation of fluorosilicone composite filler

[0054] The nanometer zirconium carbide, nanometer aluminum nitride, tridecafluoro octyl trimethoxysilane and ethanol are added into an ultrasonic tank and stirred uniformly to prepare a suspension; the ethanol is used as a dispersant and its addition amount is 10 times of the mass of the tridecafluoro octyl trimethoxysilane. The suspension is ultrasonically treated at 300 W for 40 min at a temperature of 60 ℃. The suspension after ultrasonic treatment is filtered, and the obtained solid is vacuum dried to obtain a fluorine-containing siloxane composite filler; the vacuum drying conditions are: a temperature of 90 ℃, a vacuum degree of ≤-0.08 MPa, and a drying time of 1 h.

[0055] Step three, preparation of A component

[0056] The modified boron-nitrogen heterocyclic polysiloxane, the fluorine-containing siloxane composite filler and 3-epoxypropoxypropyl triethoxysilane are added into a double planetary mixer and stirred at 90 ℃, a vacuum degree of ≤-0.08 MPa and a stirring speed of 30 r / min for 2 h. After stirring, the temperature is naturally lowered, and 2,5-dimethyl hexyne diol is added when the temperature is ≤45 ℃. After stirring uniformly, the A component is obtained.

[0057] Step four, preparation of B component

[0058] The nanometer zinc oxide and γ-methacryloyloxypropyl trimethoxysilane are uniformly mixed and then added into an ultrasonic tank and ultrasonically treated at a power of 400 W for 30 min to obtain a zinc oxide-silane reaction liquid; the zinc oxide-silane reaction liquid, hydrogen-terminated silicone oil and perfluorinated nonyl polydimethylsiloxane are added into a high-speed disperser and dispersed at a temperature of 70 ℃ and a rotating speed of 2000 r / min for 1 h to prepare the B component.

[0059] Step five, compounding and defoaming

[0060] The A component and the B component are compounded at a weight ratio of 2.8:1, and a platinum-ionic liquid catalyst is added dropwise to obtain a mixed liquid. The mixed liquid is added into a static mixer and uniformly mixed. Defoaming is performed at a vacuum degree of ≤-0.09 MPa for 20 min to prepare a high-pressure and moisture-resistant type silicone sealant.

[0061] Example 3: A high-pressure and moisture-resistant type silicone sealant for new energy power systems

[0062] A high-pressure and moisture-resistant type silicone sealant for new energy power systems is composed of an A component, a B component and a platinum-ionic liquid catalyst. The mass ratio of the A component to the B component is 3.6:1, and the amount of the platinum-ionic liquid catalyst is 0.55% of the mass of the A component.

[0063] The components of the A component include modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, 3-epoxypropoxypropyl triethoxysilane, and 2,5-dimethyl hexyne diol; the mass ratio of the modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, and 3-epoxypropoxypropyl triethoxysilane is 26.5:20:1; the amount of 2,5-dimethyl hexyne diol is 0.1 ‰ of the mass of the modified boron-nitrogen heterocyclic polysiloxane.

[0064] The components of the B component include end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane; the mass ratio of the end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane is 3:2:2:1.

[0065] The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene; the mass ratio of the octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene is 13.3:8:1.

[0066] The fluorosilicone composite filler is prepared from nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane; the mass ratio of the nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane is 2.2:6:1.

[0067] A preparation method of a high-pressure and moisture-resistant type organic silicone sealant for a new energy power system:

[0068] Step one, preparation of modified boron-nitrogen heterocyclic polysiloxane

[0069] Octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene are added to the reactor; high-purity nitrogen gas is introduced into the kettle for replacement, and the temperature is raised to 130℃ under the protection of a nitrogen atmosphere; the reaction is kept for 8h; the stirring rate is 200r / min during the whole reaction process. After the reaction is completed, the reaction liquid is subjected to vacuum distillation under the conditions of a vacuum degree ≤-0.08MPa and a temperature of 120℃; after the low-boiling substances are removed, the obtained substrate is the modified boron-nitrogen heterocyclic polysiloxane.

[0070] Step two, preparation of fluorosilicone composite filler

[0071] The nanometer zirconium carbide, nanometer aluminum nitride, tridecafluoro octyl trimethoxysilane and ethanol are added into an ultrasonic tank and stirred uniformly to prepare a suspension; the ethanol is used as a dispersant and its addition amount is 10 times of the mass of the tridecafluoro octyl trimethoxysilane. The suspension is ultrasonically treated for 60 min at a temperature of 45 DEG C and under the condition of setting an ultrasonic power of 350 W. The suspension after ultrasonic treatment is filtered, and the obtained solid is vacuum dried to obtain a fluorine-containing siloxane composite filler; the vacuum drying condition is: a temperature of 90 DEG C, a vacuum degree of less than or equal to -0.08 MPa, and a drying time of 1 h.

[0072] Step three, preparation of A component

[0073] The modified boron-nitrogen heterocyclic polysiloxane, the fluorine-containing siloxane composite filler and 3-epoxypropoxypropyl triethoxysilane are added into a double planetary stirrer and stirred for 2.5 h under the condition of a temperature of 90 DEG C, a vacuum degree of less than or equal to -0.08 MPa and a stirring speed of 30 r / min. After the stirring is completed, the temperature is naturally reduced, and then 2,5-dimethyl hexyne diol is added when the temperature is less than or equal to 45 DEG C. After uniform stirring, the A component is obtained.

[0074] Step four, preparation of B component

[0075] The nanometer zinc oxide and gamma-methacryloyloxypropyl trimethoxysilane are uniformly mixed and then added into an ultrasonic tank and ultrasonically treated for 40 min at a power of 300 W to obtain a zinc oxide-silane reaction liquid; the zinc oxide-silane reaction liquid, the hydrogen-terminated silicone oil and perfluorinated nonyl polydimethylsiloxane are added into a high-speed disperser and dispersed for 2 h under the condition of a temperature of 60 DEG C and a rotating speed of 2000 r / min to prepare the B component.

[0076] Step five, compounding and defoaming

[0077] The A component and the B component are compounded according to a weight ratio of 3.6:1, and a platinum-ionic liquid catalyst is added dropwise to obtain a mixed liquid. The mixed liquid is added into a static mixer and uniformly mixed. The mixed liquid is defoamed for 20 min under the condition of a vacuum degree of less than or equal to -0.09 MPa to prepare a high-pressure and moisture-resistant type silicone sealant.

[0078] Example 4: A high-pressure and moisture-resistant type silicone sealant for new energy power systems

[0079] A high-pressure and moisture-resistant type silicone sealant for new energy power systems is composed of an A component, a B component and a platinum-ionic liquid catalyst. The mass ratio of the A component to the B component is 3.2:1, and the amount of the platinum-ionic liquid catalyst is 0.62% of the mass of the A component.

[0080] The components of the A component include modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, 3-epoxypropoxypropyl triethoxysilane, and 2,5-dimethyl hexyne diol; the mass ratio of the modified boron-nitrogen heterocyclic polysiloxane, fluorosilicone composite filler, and 3-epoxypropoxypropyl triethoxysilane is 18:12.8:1; the amount of 2,5-dimethyl hexyne diol is 0.2 ‰ of the mass of the modified boron-nitrogen heterocyclic polysiloxane.

[0081] The components of the B component include end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane; the mass ratio of the end-hydrogen silicone oil, perfluorinated nonyl polydimethylsiloxane, nano zinc oxide, and gamma-methacryloyloxypropyl trimethoxysilane is 3.6:1.6:2.8:1.

[0082] The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene; the mass ratio of the octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene is 12.2:7.3:1.

[0083] The fluorosilicone composite filler is prepared from nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane; the mass ratio of the nano zirconium carbide, nano aluminum nitride, and tridecafluorooctyl trimethoxysilane is 4:8:1.

[0084] A preparation method of a high-pressure and moisture-resistant type organic silicone sealant for new energy power systems:

[0085] Step one, preparation of modified boron-nitrogen heterocyclic polysiloxane

[0086] Octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane, and boron-nitrogen benzene are added to the reactor; high-purity nitrogen gas is introduced into the kettle for replacement, and the temperature is raised to 130°C under the protection of a nitrogen atmosphere; the reaction is kept for 8 hours; the stirring rate is 200 r / min during the whole reaction process. After the reaction is completed, the reaction liquid is subjected to vacuum distillation under the conditions of a vacuum degree ≤-0.08 MPa and a temperature of 120°C; after the low-boiling substances are removed, the obtained substrate is the modified boron-nitrogen heterocyclic polysiloxane.

[0087] Step two, preparation of fluorosilicone composite filler

[0088] The nanometer zirconium carbide, nanometer aluminum nitride, tridecafluoro octyl trimethoxysilane and ethanol are added into an ultrasonic tank and stirred uniformly to prepare a suspension; the ethanol is used as a dispersant and its addition amount is 10 times of the mass of the tridecafluoro octyl trimethoxysilane. The suspension is ultrasonically treated for 30 min at a temperature of 60 ℃ and under the condition of an ultrasonic power of 350 W. The suspension after ultrasonic treatment is filtered, and the obtained solid is vacuum dried to obtain a fluorine-containing siloxane composite filler; the vacuum drying condition is: a temperature of 90 ℃, a vacuum degree of ≤-0.08 MPa and a drying time of 1 h.

[0089] Step three, preparation of A component

[0090] The modified boron-nitrogen heterocyclic polysiloxane, the fluorine-containing siloxane composite filler and 3-epoxypropoxypropyl triethoxysilane are added into a double planetary stirrer and stirred for 3 h at a temperature of 90 ℃, a vacuum degree of ≤-0.08 MPa and a stirring speed of 30 r / min. After the stirring is completed, the temperature is naturally reduced, and 2,5-dimethyl hexyne diol is added when the temperature is ≤45 ℃. After uniform stirring, the A component is obtained.

[0091] Step four, preparation of B component

[0092] The nanometer zinc oxide and γ-methacryloyloxypropyl trimethoxysilane are uniformly mixed and then added into an ultrasonic tank and ultrasonically treated for 40 min at a power of 400 W to obtain a zinc oxide-silane reaction liquid; the zinc oxide-silane reaction liquid, the hydrogen-terminated silicone oil and perfluorinated nonyl polydimethylsiloxane are added into a high-speed disperser and dispersed for 2 h at a temperature of 65 ℃ and a rotating speed of 2000 r / min to prepare the B component.

[0093] Step five, compounding and defoaming

[0094] The A component and the B component are combined according to a weight ratio of 3.2:1, and a platinum-ion liquid catalyst is added dropwise to obtain a mixed liquid. The mixed liquid is added into a static mixer and uniformly mixed. The mixed liquid is defoamed for 20 min under the condition of a vacuum degree of ≤-0.09 MPa to prepare a high-pressure-resistant and moisture-resistant type silicone sealant.

[0095] Comparative example 1

[0096] Step one, preparation of A component

[0097] The raw materials include, in parts by weight: 3-(N-cyclohexylamine) propyl trimethoxysilane 40 parts, nanometer zirconium carbide 12 parts, nanometer aluminum nitride 15 parts, 3-epoxypropoxypropyl triethoxysilane 0.6 parts and 2,5-dimethyl hexyne diol 0.03 parts.

[0098] 3-(N-cyclohexylamine) propyl trimethoxysilane, nano zirconium carbide, nano aluminum nitride, 3-epoxy propoxy propyl triethoxysilane were added into a double planetary mixer, and stirred at 90℃, vacuum degree ≤-0.08MPa for 2.5h, stirring speed 30r / min. After stirring, it was naturally cooled, and 2,5-dimethyl hexyne diol was added when the temperature was ≤45℃. After stirring, A component was obtained.

[0099] Step two, preparation of B component

[0100] The raw materials included 10 parts of end-hydrogen silicone oil, 5 parts of perfluoro-nonyl polydimethylsiloxane, 6 parts of nano zinc oxide, and 3 parts of γ-methacryloyloxypropyl trimethoxysilane by weight.

[0101] End-hydrogen silicone oil, perfluoro-nonyl polydimethylsiloxane, nano zinc oxide, and γ-methacryloyloxypropyl trimethoxysilane were added into a high-speed disperser, and dispersed at 65℃, 2000r / min for 2h to prepare B component.

[0102] Step three, compounding and defoaming

[0103] A component and B component were mixed at a weight ratio of 3.2:1, and platinum-ionic liquid catalyst was added dropwise to obtain a mixed solution. The mixed solution was added into a static mixer and mixed uniformly. Defoaming was performed at a vacuum degree ≤-0.09MPa for 20min to prepare silicone sealant.

[0104] The platinum-ionic liquid catalyst was composed of chloroplatinic acid and 1-butyl-3-methylimidazolium hexafluorophosphate, and the mass ratio of chloroplatinic acid to 1-butyl-3-methylimidazolium hexafluorophosphate was 1:8. The amount of platinum-ionic liquid catalyst was 0.62% of the mass of A component.

[0105] Performance test

[0106] The high-pressure and moisture-resistant silicone sealants prepared in Examples 1-4 and the silicone sealant prepared in Comparative Example 1 were tested for performance. The performance test results of Examples 1-4 and Comparative Example 1 are shown in Table 1.

[0107] Thermal conductivity (W / (m·K)): The cured sealant was made into a sheet with dimensions of 30mm×30mm×2mm. The test conditions were 23℃±2℃ and humidity 50%±5%RH. The test was performed according to GB / T 32064-2015 standard. The test results of Examples 1-4 and Comparative Example 1 are shown in Table 1.

[0108] Breakdown voltage (kV / mm): the cured sealant was made into a thin piece with a length of 30 mm, a width of 30 mm, and a thickness of 3±0.2 mm; test conditions: 23℃±2℃, humidity 50%±5%RH, and pre-placed in the test environment for 24h; tested according to GB / T 1408.1-2016 standard.

[0109] Volume resistivity (Ω·cm): the cured sealant was made into a thin piece with a diameter of 50 mm and a thickness of 2±0.2 mm; test conditions: 23℃±2℃, humidity 50%±5%RH, and pre-placed in the test environment for 24h; tested according to GB / T 1410-2006 standard.

[0110] Hygrothermal aging treatment: the prepared sealant thin piece was subjected to aging treatment according to GB / T 2423.3-2016 "Environmental testing Part 2: Test methods Test Cab: Constant humidity heat test", with a temperature of 85±1℃, a humidity of 85±3%RH, and an aging time of 1200h.

[0111] After the hygrothermal aging treatment, the sample was taken out, the surface condensate water was wiped with a dust-free cloth, and after being placed in an environment of 23±2℃, 50±5%RH for 48h, the thermal conductivity and volume resistivity were tested again, and the retention rate of each performance was calculated.

[0112] Table 1 Performance test results of examples 1-4 and comparative example 1

[0113]

[0114] From the data in Table 1, it can be seen that the thermal conductivity of the high-voltage and hygrothermal resistant silicone sealant prepared by the present application is 1.94-2.37 W / (m·K), the breakdown voltage is 38.5-40.2 kV / mm, and the volume resistivity is 2.5×10 14 ~ 3.2×10 14 Ω·cm. The above data fully show that the high-voltage and hygrothermal resistant silicone sealant prepared by the present application has better thermal conductivity and high-voltage resistance; after 1200h of hygrothermal aging treatment, the retention rates of thermal conductivity and volume resistivity are both greater than 91%, showing that it has good extreme hygrothermal weather resistance.

[0115] Obviously, there are still many specific implementation methods that can be changed under the concept of the present application, and here it should be declared that any change made under the inventive concept of the present application will fall within the protection scope of the present application.

Claims

1. A high-pressure-resistant and moisture-resistant organic silicone sealant for new energy power systems, comprising component A, component B and a platinum-ion liquid catalyst; characterized in that: The A component, component includes modified boron-nitrogen heterocyclic polysiloxane, fluorine-containing siloxane composite filler, 3-epoxy propoxy propyl triethoxysilane, 2, 5-dimethyl hexyne diol; ​ The modified boron-nitrogen heterocyclic polysiloxane is prepared from octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane and boron-nitrogen benzene; The fluorine-containing siloxane composite filler is prepared from nano zirconium carbide, nano aluminum nitride and tridecafluorooctyl trimethoxysilane; The B component, component includes end hydrogen silicone oil, perfluoro-nonyl polydimethylsiloxane, nano zinc oxide and gamma-methacryloyl propyl trimethoxysilane; The platinum-ion liquid catalyst is prepared from chloroplatinic acid and 1-butyl-3-methyl imidazole hexafluorophosphate. 2.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 1, characterized by: The mass ratio of octamethylcyclotetrasiloxane, 3-(N-cyclohexylamine) propyl trimethoxysilane and boron-nitrogen benzene is (12-13.3):(7.2-8):

1. 3.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 1, characterized by: The mass ratio of nano zirconium carbide, nano aluminum nitride and tridecafluorooctyl trimethoxysilane is (2.2-5):(6-8):

1. 4.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 1, characterized by: The mass ratio of the A component and the B component is (2.8-3.6):1, and the amount of the platinum-ion liquid catalyst is 0.55%-0.71% of the mass of the A component; The mass ratio of the amount of chloroplatinic acid and 1-butyl-3-methyl imidazole hexafluorophosphate is 1:

8. 5.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 1, characterized by: The mass ratio of the amount of end hydrogen silicone oil, perfluoro-nonyl polydimethylsiloxane, nano zinc oxide and gamma-methacryloyl propyl trimethoxysilane is (3-4):(1.5-2):(2-2.8):

1. 6.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 1, characterized by: The preparation method of the silicone sealant comprises the following steps: preparing modified boron-nitrogen heterocyclic polysiloxane, preparing fluorine-containing siloxane composite filler, preparing A component, preparing B component, and compounding and defoaming. 7.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 6, characterized by: The preparation of the fluorine-containing siloxane composite filler comprises the following steps: preparing a suspension of nano zirconium carbide, nano aluminum nitride, tridecafluorooctyl trimethoxysilane and ethanol, performing ultrasonic treatment on the suspension, filtering and vacuum drying the suspension, and obtaining the fluorine-containing siloxane composite filler; The amount of ethanol is 10 times the mass of tridecafluorooctyl trimethoxysilane; The ultrasonic treatment is performed at an ultrasonic power of 300-350 W for 30-60 min. 8.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 6, characterized by: The preparation of the A component comprises the following steps: adding modified boron-nitrogen heterocyclic polysiloxane, fluorine-containing siloxane composite filler and 3-epoxy propoxy propyl triethoxysilane into a stirrer, stirring under vacuum for 2-3 h, cooling to below 45 DEG C, adding 2, 5-dimethyl hexyne diol, and uniformly stirring to obtain the A component. 9.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 6, characterized by: The preparation of B component: after mixing nano zinc oxide and γ-methacryloxypropyl trimethoxysilane, ultrasonic treatment is carried out to obtain a zinc oxide-silane reaction solution, the zinc oxide-silane reaction solution, hydrogen-terminated silicone oil and perfluorinated nonyl polydimethylsiloxane are added into a high-speed dispersion machine and dispersed for 1-2 h to prepare the B component. 10.The high-pressure and wet-heat resistant organic silicone sealant for new energy power systems according to claim 9, characterized by: The ultrasonic treatment is carried out at an ultrasonic power of 300-400 W for 30-60 min.

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